CN108470817B - Sb-containing P-type Cu2.856In4Te8Medium-high temperature thermoelectric material and preparation process thereof - Google Patents
Sb-containing P-type Cu2.856In4Te8Medium-high temperature thermoelectric material and preparation process thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 37
- 238000003723 Smelting Methods 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 229910052738 indium Inorganic materials 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 8
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 7
- 238000000498 ball milling Methods 0.000 claims description 19
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 239000004065 semiconductor Substances 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000010453 quartz Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims 3
- 230000008018 melting Effects 0.000 claims 3
- 238000010248 power generation Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910045601 alloy Inorganic materials 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 10
- 230000002194 synthesizing effect Effects 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 238000009461 vacuum packaging Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical group [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种含Sb的P‑型Cu2.856In4Te8基中高温热电材料及其制备工艺，其设计要点是在Cu2.856In4Te8合金中直接添加摩尔分数为0.0388的Sb元素，构成含Sb的Cu2.856In4Te8基热电材料，化学式为Cu2.856Sb0.6In4Te8；其制备工艺为：根据化学式称量相应量的Cu、In、Sb、Te四种元素，在800～900℃下真空熔炼24小时。熔炼结束后冷却至390℃退火72小时，将退火后的铸锭粉碎球磨，球磨后的粉末在短时间内经放电等离子火花烧结成形，烧结时间5～10分钟，烧结温度为600～700℃，烧结压力为50～60MPa，制备得到Cu2.856Sb0.6In4Te8热电材料。该热电材料无污染，无噪音，可应用于中高温发电元器件制作，具有运行可靠，寿命长，制备工艺简单的优点。
The invention relates to a Sb-containing P-type Cu 2.856 In 4 Te 8 -based medium-high temperature thermoelectric material and a preparation process thereof. The key point of the design is to directly add Sb element with a mole fraction of 0.0388 in the Cu 2.856 In 4 Te 8 alloy, The Sb-containing Cu 2.856 In 4 Te 8 -based thermoelectric material is formed, and the chemical formula is Cu 2.856 Sb 0.6 In 4 Te 8 ; its preparation process is: according to the chemical formula, the corresponding amounts of four elements of Cu, In, Sb, and Te are weighed, and at 800 Vacuum smelting at ~900°C for 24 hours. After smelting, it was cooled to 390°C and annealed for 72 hours. The annealed ingot was pulverized and ball-milled. The ball-milled powder was sintered by spark plasma spark in a short time. The sintering time was 5-10 minutes, and the sintering temperature was 600-700°C. The pressure is 50-60 MPa, and the Cu 2.856 Sb 0.6 In 4 Te 8 thermoelectric material is prepared. The thermoelectric material is pollution-free and noise-free, can be used in the manufacture of medium and high temperature power generation components, and has the advantages of reliable operation, long service life and simple preparation process.
Description
Technical Field
The invention relates to the field of new materials, is suitable for key components and parts for medium-high temperature power generation with direct conversion of heat energy and electric energy, and is P-type Cu containing Sb2.856In4Te8A medium-high temperature thermoelectric material and a preparation process thereof.
Background
The thermoelectric semiconductor material is a novel semiconductor functional material which realizes direct interconversion of electric energy and heat energy through movement of carriers including electrons or holes. The power generation and refrigeration device made of thermoelectric material has the advantages of small volume, no pollution, no noise, no abrasion, good reliability, long service life and the like. In the civil field, the potential range of applications is: domestic refrigerators, freezers, superconducting electronic device cooling and waste heat power generation, waste heat utilization power supply, small-sized power supply devices in remote areas and the like.
The overall performance of thermoelectric materials is described by the dimensionless thermoelectric figure of merit ZT ═ T σ α2And/κ, where α is the Seebeck coefficient, σ is the electrical conductivity, κ is the thermal conductivity, and T is the absolute temperature. Therefore, the performance of the thermoelectric material has a close relationship with the temperature, and the maximum thermoelectric figure of merit (ZT) of the material is maximum only at a certain temperature value. At present, thermoelectric power generation materials for medium-temperature power generation, which have been applied to a small extent, are mainly series alloys such as Pb — Te-based, metal silicide, and the like, developed in the 50 s. The maximum thermoelectric figure of merit of the two is about 1.5, but Pb has great environmental pollution and is harmful to human bodies. The optimum use temperature for these materials is generally below 500 ℃. In the intrinsic condition, the wide bandgap Cu-In-Te ternary semiconductor material generally has large resistance, so that the thermoelectric conversion efficiency is not high, and the thermoelectric device for medium-high temperature power generation is difficult to manufacture. The main reasons for this are that the carrier concentration inside such materials is not high and the conductivity of the materials is low. However, the components and structural characteristics of some semiconductor materials with ternary chalcopyrite structures are special, and the semiconductor materials are not formed according to normal proportion, namely the Cu content in the materials is obviously lost, so that the materials have higher carrier concentration. Meanwhile, the semiconductor material with Cu deletion has higher use temperature, higher Seebeck coefficient and higher electrical conductivity under intrinsic condition. The thermal conductivity can be changed by proper element impurities, thereby greatly improving the thermoelectric property.
Disclosure of Invention
In order to overcome the problem of insufficient performance of a wide bandgap Cu-In-Te ternary semiconductor, the invention aims to provide a high-performance Sb-containing P-type Cu for the field2.856In4Te8The medium-high temperature thermoelectric material and the preparation process thereof solve the technical problems of poor thermoelectric performance and low use temperature of the existing similar materials. The purpose is realized by the following technical scheme.
One kind containsP-type Cu of Sb2.856In4Te8The medium-high temperature thermoelectric material is prepared with Cu2.856In4Te8Directly adding Sb element with the mole fraction of 0.0388 to form a quaternary Cu-In-Sb-Te thermoelectric material, wherein the chemical formula of the quaternary thermoelectric material is Cu2.856Sb0.6In4Te8. The thermoelectric material is prepared by adopting a conventional powder metallurgy method, and the preparation process comprises the following steps: according to the chemical formula Cu2.856Sb0。6In4Te8Proportioning four elements of Cu, In, Sb and Te, directly putting into a quartz tube for vacuum packaging, and then carrying out smelting synthesis. The smelting synthesis temperature is 800-900 ℃, and the synthesis time is 20-28 hours. Cooling to 390 ℃ after smelting synthesis for annealing for 72 hours, crushing and ball milling the annealed cast ingot for 5 hours, sintering and forming the powder subjected to ball milling drying in a short time by spark discharge plasma spark for 5-10 minutes at the sintering temperature of 600-700 ℃ and the sintering pressure of 50-60 MPa, and preparing to obtain the Cu2.856Sb0.6In4Te8A thermoelectric material.
In the above preparation process, the Cu2.856Sb0.6In4Te8The preferred smelting synthesis temperature of the thermoelectric material is 850 ℃, the sintering temperature is 650 ℃, the sintering pressure is 55MPa, and the sintering time is 8 minutes.
The invention has the advantages that: when the Sb-containing P-type medium-high temperature thermoelectric material obtained by the preparation process is 870K, the Seebeck coefficient alpha of the material is 191.10 (mu V/K), and the electric conductivity sigma is 1.76 multiplied by 104Ω-1.m-1Thermal conductivity k is 0.36 (W.K)-1.m-1) The maximum thermoelectric figure of merit ZT is 1.55, which is a material with better performance In the Cu-In-Te base medium-high temperature thermoelectric material reported at present. The material adopts a conventional preparation process, a proper amount of Sb element is added, the cost is low, the material can be applied to manufacturing of medium-high temperature power generation components, and the manufactured thermoelectric conversion device has the characteristics of no noise, no pollution, reliable operation and long service life. Is suitable for being used as an environment-friendly thermoelectric material.
Drawings
FIG. 1 is a schematic representation of thermoelectric performance of the present invention compared to other materials.
The ordinate in the above figures is the thermoelectric figure of merit ZT; the abscissa is the temperature T/K; and the chemical composition is indicated in relation to the examples by different labels.
Detailed Description
The invention will be further described in the following with reference to specific embodiments thereof, in conjunction with the accompanying drawings.
Cu2.856Sb0.6In4Te8Absolute Seebeck coefficient of (a) from 142.6(μ V.K) around room temperature-1) Increase to 195.96(μ V.K) at 831.2K-1) Then gradually decreased to 191.10(μ V.K) at 870K-1). Conductivity of 2.22X 10 from the vicinity of room temperature4Ω-1.m-1Increased to 694K to 3.28X 104Ω-1.m-1Then decreases to 1.76X 10 at 870K with temperature4Ω-1.m-1. Total thermal conductivity from 2.32 (WK)-1m-1) Monotonically decreasing to 0.36 (WK) at 870K-1m-1). The comprehensive thermoelectric performance of the medium-high temperature thermoelectric material is maximum when T is 870K, and the maximum thermoelectric figure of merit is ZT 1.55.
Example 1:
according to the chemical formula Cu2.856In4Te8Weighing ternary element particles of Cu, In and Te with the purity of more than 99.999 wt.% and directly placing the ternary element particles In a quartz tube for vacuum packaging. Then smelting and synthesizing for 24 hours at 850 ℃, cooling to 390 ℃ after smelting and synthesizing for annealing for 72 hours, crushing and ball-milling the annealed ingot, controlling the ball-milling time to be 5 hours, sintering and forming the powder after ball-milling and drying in a short time by spark sintering of discharge plasma at the sintering temperature of 650 ℃ and the sintering pressure of 55MPa, and preparing the Cu2.856In4Te8A thermoelectric material.
Example 2:
according to the chemical formula Cu2.856Sb0.25In4Te8Weighing four-element particles of Cu, Sb, In and Te with the purity of more than 99.999 wt.% and directly placing the four-element particles In a quartz tube for vacuum packaging. Then smelting at 850 deg.CSynthesizing for 24 hours, cooling to 390 ℃ after smelting and synthesizing for annealing for 72 hours, crushing and ball-milling the annealed ingot, controlling the ball-milling time to be 5 hours, sintering and forming the powder subjected to ball-milling drying in a short time by spark discharge plasma spark sintering, wherein the sintering time is 8 minutes, the sintering temperature is 650 ℃, and the sintering pressure is 55MPa, and preparing the Cu2.856Sb0.25In4Te8A thermoelectric material.
Example 3:
according to the chemical formula Cu2.856Sb0.5In4Te8Weighing four-element particles of Cu, Sb, In and Te with the purity of more than 99.999 wt.% and directly placing the four-element particles In a quartz tube for vacuum packaging. Then smelting and synthesizing for 24 hours at 850 ℃, cooling to 390 ℃ after smelting and synthesizing for annealing for 72 hours, crushing and ball-milling the annealed ingot, controlling the ball-milling time to be 5 hours, sintering and forming the powder after ball-milling and drying in a short time by spark sintering of discharge plasma at the sintering temperature of 650 ℃ and the sintering pressure of 55MPa, and preparing the Cu2.856Sb0.5In4Te8A thermoelectric material.
Example 4:
according to the chemical formula Cu2.856Sb0.6In4Te8Weighing four-element particles of Cu, Sb, In and Te with the purity of more than 99.999 wt.% and directly placing the four-element particles In a quartz tube for vacuum packaging. Then smelting and synthesizing for 24 hours at 850 ℃, cooling to 390 ℃ after smelting and synthesizing for annealing for 72 hours, crushing and ball-milling the annealed ingot, controlling the ball-milling time to be 5 hours, sintering and forming the powder after ball-milling and drying in a short time by spark sintering of discharge plasma at the sintering temperature of 650 ℃ and the sintering pressure of 55MPa, and preparing the Cu2.856Sb0.6In4Te8A thermoelectric material.
Example 5:
according to the chemical formula Cu2.856Sb0.7In4Te8Weighing four-element particles of Cu, Sb, In and Te with the purity of more than 99.999 wt.% and directly placing the four-element particles In a quartz tube for vacuum packaging. Then smelting and synthesizing for 24 hours at 850 ℃, cooling to 390 ℃ after smelting and synthesizing for annealing for 72 hours, and cooling to obtain the final productCrushing and ball-milling the annealed cast ingot, controlling the ball-milling time to be 5 hours, sintering and forming the powder subjected to ball-milling drying in a short time by spark sintering of discharge plasma at the sintering temperature of 650 ℃ and the sintering pressure of 55MPa to prepare the Cu2.856Sb0.7In4Te8A thermoelectric material.
Seebeck coefficient (. mu. V.K) of the material obtained in each of the above examples-1) Conductivity (omega)-1m-1) Thermal conductivity (WK)-1m-1) Thermoelectric figure of merit (ZT) is shown in table one below:
watch 1
As is clear from the above Table I, the thermoelectric material (Cu) produced in example 4 of the present invention2.856Sb0.6In4Te8) The medium-high temperature thermoelectric material has the best thermoelectric performance, adopts the conventional powder metallurgy preparation process, has low cost and has practical application value.
Claims (3)
1. Sb-containing P-type Cu2.856In4Te8A medium-high temperature thermoelectric material, characterized in that Cu is used as a material2.856In4Te8Sb element with a mole fraction of 0.0388 is directly added to the semiconductor to form Sb-containing Cu2.856In4Te8A base thermoelectric material having a chemical formula of Cu2.856Sb0.6In4Te8。
2. Sb-containing P-type Cu2.856In4Te8The preparation process of medium-high temperature thermoelectric material is characterized by that said preparation process is according to chemical formula Cu2.856Sb0.6In4Te8Putting four elements of Cu, In, Sb and Te into a quartz tube for vacuum melting synthesis, wherein the melting synthesis temperature is 800-900 ℃, the synthesis time is 20-28 hours, and the temperature is reduced to 390 ℃ after melting synthesis for annealing for 72 hoursCrushing and ball-milling the annealed cast ingot for 5 hours, sintering and forming the powder subjected to ball-milling drying in a short time by spark sintering of discharge plasma, wherein the total sintering time is 5-10 minutes, the sintering temperature is 600-700 ℃, the sintering pressure is 50-60 MPa, and the Cu is prepared2.856Sb0.6In4Te8A thermoelectric material.
3. The Sb-containing P-type Cu according to claim 22.856In4Te8The preparation process of the medium-high temperature thermoelectric material is characterized in that the Cu2.856Sb0.6In4Te8The smelting synthesis temperature of the thermoelectric material is 850 ℃, the sintering temperature is 650 ℃, the sintering pressure is 55MPa, and the sintering time is 8 minutes.
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